Revealing Disorder, Sorption Locations and a Sorption-Induced Single Crystal-Single Crystal Transformation in a Rare-Earth -Type Metal-Organic Framework.

Rare-earth metal-organic frameworks (RE-MOFs) formed in the presence of fluoride donors are a group of complex and applicable MOFs. Determining structural complexity is crucial in applying such MOFs and has been achieved to uncover framework disorders in the important framework topology MOF, Y-ndc--MOF (). is found to contain F groups disordered over the μ-face-capping sites in its secondary building unit (SBU) and framework distortions upon sorption of different guest molecules. The favored location of the guests is within the octahedral cage of where they interact with the Y centers. The size, shape, and interactions of the different guests lead to subtle distortions within the SBU and adoption of specific orientations of the naphthalene group of the 1,4-naphthalenedicarboxylate framework linkers. The sorption of DMF/HO lowers the symmetry from cubic 3̅ (for MeOH, N, CO) to cubic 3̅ (for DMF/HO) symmetry with retention of the topology, and conversion between the 3̅ and 3̅ structures is induced by solvent exchange. Such disorder and sorption locations and transformation are important considerations during the optimization and application of MOFs for sorption-based technologies.